Gradient Structural Bone-Like Apatite Induced by Chitosan Hydrogel via Ion Assembly

Abstract

Polymers with negatively charged groups (−COOH, −OH or −PO4H2) were frequently adopted to induce or promote apatite deposition through electrostatic interaction. However, chitosan with positively charged groups (−NH2) was ignored, although it could bind most of metal ions through chelation. Based on the chelation properties of the amino group, a chitosan hydrogel obtained via physical cross-linking was used as template for ion assembly. Gradient structural bone-like apatite induced by chitosan hydrogel was achieved via ion assembly within a few hours under ambient conditions, in which amino groups of chitosan acted as anchors between chitosan and apatite nucleation. The phase and component of bone-like apatite were similar to apatite in rabbit ribs according to XRD patterns and FT-IR spectra. XRD results revealed that bone-like apatite was carbonated apatite and preferred growth orientation in the direction of c-axis. The profile of elements distribution in chitosan suggested that the content of calcium and phosphorous elements decreased with the increase of depth along the radius direction, which was accompanied by the formation of apatite-rich regions near the outer layer. When chitosan was dipped in calcium ions solution, Ca2+ ions bound amino groups of chitosan and formed chitosan/calcium ions complexes (CS–NH2…Ca2+). CS–NH2…Ca2+ subsequently attracted negatively-charged phosphate ions through electrostatic interaction. When ion assembly finished, Ca and P ions in the chitosan hydrogel converted into ACP with Ca/P ratio of 1.19. ACP converted into bone-like apatite with Ca/P ratio of 2.01 after alkali treatment.